CN103874539A - Fischer-tropsch catalyst comprising cobalt, magnesium and precious metal - Google Patents
Fischer-tropsch catalyst comprising cobalt, magnesium and precious metal Download PDFInfo
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- CN103874539A CN103874539A CN201280050291.4A CN201280050291A CN103874539A CN 103874539 A CN103874539 A CN 103874539A CN 201280050291 A CN201280050291 A CN 201280050291A CN 103874539 A CN103874539 A CN 103874539A
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- catalyst
- method described
- cobalt
- compound
- calcining
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 239000011777 magnesium Substances 0.000 title claims abstract description 43
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 26
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000010970 precious metal Substances 0.000 title claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 title description 29
- 239000010941 cobalt Substances 0.000 title description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000000034 method Methods 0.000 claims abstract description 58
- 238000001354 calcination Methods 0.000 claims abstract description 40
- 230000007704 transition Effects 0.000 claims abstract description 23
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000007598 dipping method Methods 0.000 claims description 23
- 230000009467 reduction Effects 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- 229910000510 noble metal Inorganic materials 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 6
- 239000002955 immunomodulating agent Substances 0.000 claims description 5
- 229940121354 immunomodulator Drugs 0.000 claims description 5
- 230000002584 immunomodulator Effects 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052622 kaolinite Inorganic materials 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 6
- 239000012018 catalyst precursor Substances 0.000 abstract description 5
- 235000013495 cobalt Nutrition 0.000 description 29
- 239000000463 material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003426 co-catalyst Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 3
- -1 magnesium aluminate Chemical class 0.000 description 3
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 102100022840 DnaJ homolog subfamily C member 7 Human genes 0.000 description 2
- 101000903053 Homo sapiens DnaJ homolog subfamily C member 7 Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 108091034341 Gamma family Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007937 lozenge Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/0207—Pretreatment of the support
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- B01J37/02—Impregnation, coating or precipitation
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- B01J37/0242—Coating followed by impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
A method is described for preparing a catalyst precursor suitable for use in the Fischer-Tropsch synthesis of hydrocarbons comprising 10 to 40%by weight of cobalt oxide crystallites and 0.0 to 0.5% by weight of a precious metal promoter, dispersed over the surface of a porous transition alumina wherein the surface of the transition alumina has been modified by inclusion of 0.25 to 3.5% wt magnesium, comprising the steps of: (a)forming a modified catalyst support by impregnating a transition alumina with a magnesium compound, drying and calcining the impregnated alumina in a first calcination at a temperature <=600 o C to convert the magnesium compound into oxidic form, and (b)forming a catalyst precursor by impregnating the modified catalyst support with a cobalt compound and precious metal promoter compound, drying and calcining the impregnated catalyst support ina second calcination to convert the cobalt compound to cobalt oxide.
Description
The present invention relates to Co catalysts and particularly load on the Co catalysts of the noble metal promoted in the transition alumina of modification, it is applicable in the Fischer-Tropsch of the hydrocarbon of high temperature synthetic.
The cobalt Fischer-Tropsch catalysts that loads on the noble metal promoted on titanium dioxide, aluminium oxide or silica is known.US4088671 discloses a kind of hydrocarbon synthesis process, and it uses Ru on different carriers to help the Co catalyst of catalysis.US4493905 discloses the fluid catalyst that is suitable for Fischer-Tropsch reaction, it is as the preparation of getting off: by contacting containing water soaking solution of aluminium oxide in small, broken bits and cobalt salt, the dry carrier through dipping, contacts with ruthenium this carrier thereafter with non-moisture organic dipping solution of IIIB family or IVB family metal.US4822824 discloses Ru on titanium dioxide helps the Co catalyst of catalysis.
US5302622 discloses a kind of method of synthetic hydrocarbon, and it has used the catalyst of the cobalt, copper and the ruthenium that are included on silica or aluminium oxide.This catalyst can be used as oxidation precursor and provides and revert at Fischer-Tropsch reaction device situ their activity form, or can provide to reactor the catalyst of prereduction, that it has a passivation or be encapsulated in the simple substance cobalt in wax.
The problem that uses these catalyst often to occur is the rapid deactivation at high temperature in using, particularly all the more so in the time of the temperature operation of >=230 ℃.
WO2005/072866 describes a kind of method of the catalyst of producing alumina load, and it comprises the following steps: the first impregnation steps, therein by the source dipping that can form with aluminium oxide the divalent metal of spinel compound for initial alumina supporting material; The first calcining step, calcines to produce the alumina supporting material of modification through the alumina supporting material of dipping therein the temperature of at least 550 ℃; The second impregnation steps, therein the source dipping with catalytically-active metals by the alumina supporting material through modification; With the second calcining step, the temperature calcining at least 150 ℃ by the carrier material of the modification through dipping therein.This catalytically-active metals can be cobalt; The source of divalent metal can comprise the source of cobalt, zinc, magnesium, manganese, nickel or iron, and can have the co-catalyst that comprises platinum, iridium, ruthenium or rhenium.But what this open source literature was paid close attention to is to improve abrasion performance, and test comprise 5 or 10% magnesium containing magnesium material, and form the temperature calcining of magnesium aluminate at reactive magnesium.Whole shows the relative activity of going on business containing Mg catalyst.
Similarly, US7071239 discloses Fischer-Tropsch process and catalyst, and it has used the carrier in the stabilisation based on boehmite of high-temperature calcination.Preferred structural stabilizing agent can comprise element for example cobalt, magnesium, zirconium, boron, aluminium, barium, silicon, lanthanum, its oxide or its combination, or can comprise the silica-alumina of for example co-precipitation of precipitated oxides.
We have found that and use the combination of noble metal promoted agent and magnesium-modified alumina support (wherein magnesium exists with low-level, and in lower temperature preparation), the cobalt Fischer-Tropsch catalysts forming has activity and the stability of raising in Fischer-Tropsch reaction, particularly all the more so at high temperature.
Therefore the invention provides the method for the synthetic catalyst precarsor of a kind of Fischer-Tropsch for the preparation of being applicable to hydrocarbon, the cobalt oxide crystallite that this catalyst precarsor comprises 10-40wt% and the noble metal promoted agent of 0.05-0.5wt%, it is dispersed on the surface of porous transition alumina, wherein modification is carried out by the magnesium of including 0.25-3.5wt% in the surface of this transition alumina, and the method comprises the following steps:
(a) form through the catalyst carrier of modification as got off: flood transition alumina with magnesium compound, in the first calcining the temperature of≤600 ℃ dry and calcining through the aluminium oxide of dipping, so that magnesium compound is changed into oxidised form, and
(b) form catalyst precarsor as got off: use cobalt compound and the noble metal promoted immunomodulator compounds dipping catalyst carrier through modification, the dry and catalyst carrier of calcining through flooding in the second calcining, to change into cobalt oxide by cobalt compound.
The present invention further provides a kind of method of Kaolinite Preparation of Catalyst, it comprises the step of reducing catalyst precursor.
Therefore the present invention includes catalyst and the catalyst precarsor that can obtain by these methods.
The present invention further provides a kind ofly for the synthetic method of the Fischer-Tropsch of hydrocarbon, it comprises the step that the syngas mixture that comprises hydrogen and carbon monoxide is contacted in Fischer-Tropsch reaction device with this catalyst.
The content of magnesium of catalyst precarsor is 0.25-3.5wt%, preferred about 1.0-3.0wt%, most preferably from about 1.5-2.5wt%.Have been found that for example about 4wt% of higher level has serious inactivating effect for the activity of formed catalyst.Because calcining heat used is relatively low, at least part of magnesium in catalyst precarsor exists as magnesia MgO.There is not magnesium aluminate in the XRD analysis demonstration of the aluminium oxide of Mg modification.Because the amount of the magnesium for modified aluminas is relatively low, therefore only the surface of aluminium oxide is modified, and the body phase performance of aluminium oxide remains unchanged to a great extent like this.Magnesium may reside in the hole of transition alumina and on outer surface.
The cobalt content of catalyst precarsor can be 10-40wt%, and preferably 15-30wt%, to suppress the number of dipping in manufacture process.Promoter metal can be selected from one or more in Pt, Pd, Re, Ru, Ir or Au, but Ru is particularly preferred.And the amount of co-catalyst can be 0.05-0.5wt%, the optimised quantity that has been found that co-catalyst is 0.05-0.25wt%, preferably 0.05-0.20wt%, and it is starkly lower than the amount in many catalyst of testing above.Lower co-catalyst level obviously has useful processing and cost implication.
Cobalt, noble metal promoted agent and the amount of magnesium in catalyst precarsor can be used known method easily to determine, for example ICP-atomic emission spectrometry (ICP-AES) or x-ray fluorescence method (XRF).
Transition alumina can be gamma oxidation aluminium family, for example η-aluminium oxide or χ-aluminium oxide.These materials can form by calcining aluminium hydroxide at 400-750 ℃, and conventionally have 120-400m
2the BET surface area of/g.Alternatively, transition alumina can be δ-oxidation aluminium family, and it comprises for example δ of high temperature form that can form to more than approximately 800 ℃ temperature by heating γ family aluminium oxide-and θ-aluminium oxide.δ family aluminium oxide has 50-150m conventionally
2the BET surface area of/g.In the present invention, preferably to comprise BET surface area be 120-170m to transition alumina
2the gamma-alumina of/g and/or δ aluminium oxide.In the situation that catalyst precarsor uses gamma-alumina to prepare, can its at least a portion be changed into δ aluminium oxide by calcining and reducing program.Therefore catalyst precarsor can be prepared with gamma-alumina, and the cobalt crystallite that catalyst comprises noble metal promoted, its be dispersed in gamma-alumina, δ aluminium oxide or comprise δ and the mixing phase material of gamma-alumina on.Aluminium oxide should be in being suitable for use as the purity of catalyst carrier.Particularly, the level of alkali metal in aluminium oxide, particularly sodium <50ppm ideally, more preferably <10ppm.Be to be understood that the present invention's transition alumina used is for example, from hydrated alumina (hibbsite) and boehmite very different in performance and behavior.
Conventionally there is the volume median diameter D[v of 1-200 μ m for the suitable alumina powder of catalyst carrier, 0.5].Some application examples as the catalyst for being used in slurry reaction in, advantageously use very fine particle, its volume median diameter D[v, 0.5] be 1-30 μ m, for example 5-25 μ m.For other application examples as catalyst for the reaction carried out at fluid bed, expectation be to use larger granularity, preferably 50-150 μ m.Term volume median diameter D[v, 0.5] (sometimes write D
50or D
0.5) can be calculated by grain size analysis, it can for example be undertaken by laser diffraction with Malvern Mastersizer expediently.
The pore volume of alumina support is preferably relatively high, and object is to carry out cobalt load.The pore volume of aluminium oxide is preferably 0.30cm
3more than/g, be more preferably 0.35-0.85cm
3/ g, and can measure by nitrogen physical absorption by known technology.Preferably alumina support has relatively large average pore size, because it is particularly preferred selective to use such carrier can give catalyst.The average pore size (APD) of preferred carrier is at least 10nm, particularly 12-25nm.[representing by the measured pore volume of the absorption branch of the nitrogen physisorption isotherms at 0.99 relative pressure, divided by BET surface area, to be multiplied by 4 by term average pore size].
Transition alumina it is desirable to powder type, but can be also pellet or the extrudate being shaped.
In powder type, for example as spray-dired powder, the catalyst precarsor forming can be for slurry phase Fischer-Tropsch reaction device.Catalyst precursor powder also can be shaped as pellet or extrudate, or for the preparation of the washcoat that is suitable for metallizing or ceramic monolith structure.In for example pellet of form being shaped or extrudate, catalyst precarsor goes for fixed bed Fischer-Tropsch reaction device.In coated form, for example as metal or the structural washcoat of ceramic monolith, catalyst can be in micro passage reaction.
In the catalyst of activation, at least part of cobalt oxide (Co in catalyst precarsor
3o
4) be reduced into simple substance cobalt.When in reduction-state, catalyst comprises cobalt crystallite, and its desirable average-size is 6-14nm, preferably 6-10nm.This can measure by XRD analysis or by cobalt surface area measurement, and it can compatibly adsorb to measure by Hydrochemistry.
Catalyst in reduction-state can be difficult to process, because their meetings and airborne oxygen spontaneous reaction, this can cause less desirable Automatic-heating and loss of activity.Therefore the catalyst of reduction is preferably protected by the catalyst granules of sealing this reduction with suitable barrier coat.In the situation of Fischer-Tropsch catalyst, this can be compatibly chloroflo.According to known method, catalyst can provide with the form of pellet, lozenge or thin slice.Alternatively, the slurry that catalyst can be used as in molten wax provides.
The method of Kaolinite Preparation of Catalyst carrier comprises: the catalyst carrier that (a) forms modification as got off: flood transition alumina with magnesium compound, in the first calcining, be dried and the aluminium oxide of calcining through flooding the temperature of≤600 ℃, so that magnesium compound is changed into oxidised form, (b) form catalyst precarsor as got off: use cobalt compound and the noble metal promoted immunomodulator compounds dipping catalyst carrier through modification, dry and the catalyst carrier of calcining through flooding in the second calcining, to change into cobalt oxide by cobalt compound.
In dipping method, applicable soluble metal compound (for example metal nitrate or acetate) can for example, be impregnated into carrier material from the aqueous solution or non-aqueous solution (ethanol) (it can comprise other materials), then dry one or more solvents of removing.One or more soluble metal compounds may reside in this solution.Can carry out one or more impregnation steps and improve content of metal.Dipping can be undertaken by known to the skilled any method that catalyst is manufactured field, but preferably undertaken by so-called " dry method " or " initial wetting " dipping, because this minimizes the used amount with the solvent that need to remove in dry.Incipient wetness impregnation comprises mixes carrier material with the solution that is only enough to the hole of filling carrier.In the present invention, 150% of preferred initial wetting volume at the most amount.
Magnesium compound can be any applicable soluble magnesium compound, but preferably relatively easily changes into magnesia by heating, and can not leave the magnesium compound that may cause the residue of less desirable side reaction in poisoning or Fischer-Tropsch process.A kind of particularly preferred magnesium compound is magnesium nitrate, and it is administered in transition alumina as the aqueous solution aptly.Single impregnation is enough to providing required content of magnesium conventionally in the catalyst precarsor of calcining.
If needed, the aluminium oxide through dipping is for example, at air or inert gas (nitrogen) lower dry.Dry can carry out the environment temperature of approximately 20 ℃ except desolventizing, but preferably carry out 1-8 hour the temperature of 90-120 ℃.Also can use vacuum drying.Alternatively, drying steps can be used as the initial portion of method for calcinating being applied on the aluminium oxide of dipping and assigns to carry out.
The first calcining should be carried out at≤600 ℃, preferably≤550 ℃ or even≤540 ℃, do not change into magnesium aluminate spinels to make decomposing by magnesium compound the magnesia being formed.For example, although calcining can be carried out under inert gas (nitrogen), it preferably carries out under air.The first calcining is carried out the temperature of >=250 ℃ aptly, preferably >=350 ℃, most preferably >=450 ℃ to make magnesium compound substantially complete to magnesian conversion, and is not excessively tediously long.Common the first calcining can, by within the time of 1-6 hour, temperature is elevated to maximum temperature, and carry out the time that is retained to how about 6 hours at this.
Then can process with cobalt and precious metal chemical complex through magnesium-modified aluminium oxide.For example generally include, by the solution phase combination of the cobalt acetate of catalyst carrier and debita spissitudo and/or cobalt nitrate (cabaltous nitrate hexahydrate (II)) for the production of the dipping method of Co catalysts.And can use many solvents, for example water, alcohol, ketone or their mixture, preferably use cobalt nitrate aqueous solution to flood in the carrier through modification.Use cabaltous nitrate hexahydrate, can come " from solubilize " by material being warmed up to approximately 60 ℃ (now cobalt nitrate is dissolved in its crystallization water).Preferably repeat this dipping and dry, until the cobalt content of the catalyst precarsor through calcining is 15-30wt%.
Noble metal promoted agent also, by dipping, is used for example nitrate of suitable soluble compound (it comprises nitrosyl radical nitrate), chloride, acetate or their mixture and is included in catalyst precarsor.Preferably this noble metal promoted immunomodulator compounds is the compound of Pt, Pd, Re, Ru, Ir or Au, and repeats this dipping, until the bullion content of dry catalyst precarsor is 0.05-0.5wt%, and preferably 0.05-0.2wt%.In a preferred embodiment, this precious metal chemical complex is Ru compound.Can use ruthenium acetate, preferably nitrosyl radical nitric acid ruthenium.
Cobalt compound and precious metal chemical complex can flood simultaneously or in succession.Therefore, co-catalyst can be included in catalyst precarsor before or after cobalt, or by cobalt and cocatalyst compound being incorporated in identical dipping solution and be included in catalyst precarsor simultaneously.When having been found that cobalt and noble metal promoted agent, total immersion stain is carried out well especially in the present invention.
As the carrier for through magnesium-modified, drying steps can descend or carry out in vacuum drying oven at 20-120 ℃ in air or for example, at inert gas (nitrogen).Equally, catalyst precarsor can be dried to remove desolventizing before the second calcining, or calcined and be dried and cobalt compound is changed into oxidised form with second.Before the second calcining, catalyst precarsor can be in low temperature precalcining, particularly after the first cobalt dipping second or further cobalt before flooding, carry out.Such precalcining is preferably by after drying steps, and the temperature time of lasting 1-6 hour that is warmed up to 200-300 ℃ carries out.The second calcining can, in air or inert gas, be carried out the temperature of 250-650 ℃, preferably 450-650 ℃, more preferably 450-550 ℃.Calcination time preferably≤24 hours, more preferably≤16 hours, most preferably≤8 hours, particularly≤6 hours.Conventionally, the second calcining can be by within the time of 1-6 hour, and the time that is warmed up to maximum temperature and is retained to how about 6 hours at this carries out.
In order to give the catalytic activity of catalyst precarsor for Fischer-Tropsch reaction, cobalt oxide can be reduced into cobalt metal at least partly.This reduction step can be carried out with being selected from following reducing gas: the mixture of hydrogen, synthesis gas or hydrogen and/or carbon monoxide and nitrogen or other inert gases.It is hydrogeneous and/or containing the gas of carbon monoxide that operable preferred reducing gas stream comprises.Reduction is preferably used hydrogen-containing gas to carry out in the temperature raising.The hydrogen that preferably this reducing gas stream comprises >25vol%, more preferably >50vol%, most preferably >75vol%, particularly >90vol%.In reduction phase, reducing gas stream and the therefore preferably 350-500 ℃ of temperature of catalyst precarsor.Recovery time preferably≤24 hours, more preferably≤16 hours, most preferably≤8 hours, particularly≤6 hours, and the minimum recovery time be approximately 2 hours.
Preferably at least 60% cobalt is reduced, reduction degree (DOR) preferably >=60%, more preferably >=75%, particularly >=80%.Can be as the use of getting off for assessment of temperature programmed reduction (TPR) method of DOR:
1. with 10 ℃/min, sample temperature is increased to required reduction temperature steadily, and keeps 7 hours (TPR1) in this temperature.
2. do not cool back room temperature, sample temperature is warmed up to 1000 ℃ with 10 ℃/min, and keep 10 minutes (TPR2) at 1000 ℃.This reduces whole cobalts completely.
3. integrate from TPR1 and 2 collected hydrogen.Ratio TPR1/ (TPR1+TPR2) is reduction degree (being expressed as %).
Reduction can be carried out under the pressure of environmental pressure or raising, and the pressure of reducing gas can be suitably 1-50 bar absolute pressure, preferably 1-20 bar absolute pressure, more preferably 1-10 bar absolute pressure.
The gas space-time speed (GHSV) of reducing gas stream can be 100-25000h
-1, preferably 1000-15000h
-1.
Before reduction step, if needed, drying or the catalyst precarsor through calcining can use method known to those skilled in the art, form and are suitable for the forming unit that this catalyst will be used for method wherein.This forming unit can be aggregation, pellet or extrudate, and it can be spherical, cylindrical, annular or multi-hole granule, and it can be multi-leaf-shaped or reeded, for example, have quatrefoil cross section.
After reduction, due to the reactivity of cobalt metal and airborne oxygen, preferably further comprise and will be encapsulated in the step in chloroflo through the catalyst of reduction for the preparation of the method for catalyst.
This catalyst can be synthetic for the Fischer-Tropsch of hydrocarbon.It is known that the Fischer-Tropsch of the hydrocarbon of use Co catalysts is synthesized.Fischer-Tropsch is synthetic changes into hydrocarbon by the syngas mixture that comprises carbon monoxide and hydrogen.The typical hydrogen of synthesis gas: carbon monoxide ratio is 1.6-3.0:1, preferably 1.8-2.2:1.This reaction can be in continuous or discontinuous method, and using one or more fixed bed reactors, micro passage reaction (is that catalyst is positioned at the common <150mm of cross-sectional area
2passage in reactor), conventional stirring-type slurry phase reactor, jet loop reactor, bubbling column reactor or fluidized-bed reactor carry out.The method can be clung to the pressure of absolute pressure and the temperature operation of 150-260 ℃ at 10-60.For continued operation, gas space-time speed (GHSV) can be 100-25000h
-1.Preferred opereating specification is 1000-20000h
-1.
Catalyst of the present invention has demonstrated the stability in the increase of high running temperature, especially the temperature of the temperature of 200-260 ℃, particularly 230-260 ℃.For the temperature of 230-250 ℃, the method can be with CO conversion ratio more than 40%, and C5+ hydrocarbon-selective >=80% and methane selectively≤15% (preferably≤10%) move.This selectivity and stability (being C5+ hydrocarbon-selective stability and methane selectively stability) has been proved to be 24 hours or longer.Do not there is the corresponding catalyst that magnesia helps catalysis or have higher level magnesium and do not demonstrate identical selectivity and stability.Under identical flow velocity, temperature and pressure condition, can realize more than 0.8 and more than 0.9 conversion ratio stability even, it is defined as initial CO conversion ratio (before >=210 ℃ of operations) divided by final CO conversion ratio (at >=210 ℃, particularly after 230 ℃ of-260 ℃ of operations).
Further describe the present invention referring now to the following examples with reference to figure 1,2 and 3.
embodiment 1: Kaolinite Preparation of Catalyst precursor
A) carrier.Commercially available transition alumina powder (Puralox100/150) is used to initial wetting method, flood with magnesium nitrate hexahydrate (MgNHH) aqueous solution.Then this moist material is spread on stainless steel pallet, and in air in 550 ℃ calcining 5 hours, heating rate is 5 ℃/min.Manufactured three kinds of modified supports, nominal has been used the Mg of Mg, 3wt% and the Mg of 6wt% as a comparison of 0.5wt%.Consumption is:
The Puralox100/150 of the Mg-39.6g of embodiment 1a:0.5%, the MgNHH of 2.7g, 42.5mL deionized water.
The Puralox100/150 of the Mg-38.5g of embodiment 1b:3%, the MgNHH of 15.9g, the deionized water of 32.5mL.
Comparative example A: the Puralox100/150 of 6% Mg-36.9g, the MgNHH of 31.6g, 20.8mL deionized water.
B) catalyst precarsor.By the aqueous solution of whole three kinds of cabaltous nitrate hexahydrates for modified support (CoNHH) and nitrosyl radical nitric acid ruthenium (RuNN), carry out total immersion stain by initial wetting, there is the catalyst precarsor of the Co of 20wt% and the Ru of 0.1wt% to produce nominal.Consumption is the CoNHH of 49.50g, the RuNN of 0.16g and appropriate deionized water (Mg of Mg, 3wt% and the Mg material of 6wt% for 0.5wt% are respectively 14.0mL, 6.0mL and 2.5mL).This moist material is spread on stainless steel pallet, and 250 ℃ of calcinings 8 hours, heating rate was 5 ℃/min.In addition, produce contrast material comparative example B by identical method, the Co that it contains the nominal 20% on Puralox100/150 and 0.1% Ru.
As follows containing the elementary analysis on Mg material at three kinds by XRF:
| Sample | Co | Al | Mg | Ru |
| Embodiment 1a | 17.18 | 36.86 | 0.26 | 0.06 |
| Embodiment 1b | 19.58 | 33.28 | 2.06 | 0.06 |
| Comparative example A | 18.26 | 31.07 | 4.13 | 0.05 |
Cobalt surface area adsorbs to measure with above-mentioned Hydrochemistry.
The temperature programmed reduction (TPR) carrying out on catalyst precarsor has shown two main peaks in whole figure, and it is corresponding to Co
3o
4arrive CoO and the CoO transformation to Co metal.Along with the increase of Mg content, the maximum at two peaks is moved to higher temperature, and at Co
3o
4on-CoO peak, there is low temperature shoulder.And along with the increase of Mg load capacity, particularly until 3% Mg load capacity, the area below described peak also increases, and this shows to have more substantial reducible cobalt through the material of Mg modification, but, for higher Mg load capacity, this cobalt only temperature more than 500 ℃ reduces.
embodiment 2: catalyst test
A) GHSV changing.Carry out detecting catalyst by each precursor of about 0.134g being placed in the chamber of microreactor test cell.By catalyst at 425 ℃ at H
2with reduction in Ar stream, then cool to 160 ℃.Now, introduce CO to form H
2: CO, than the syngas mixture for 2:1, is 20 bar by pressure setting, then uses the programming rate of 0.1 ℃/min to be progressively warmed up to 210 ℃.Use 30ml
n/ minute synthesis gas flow velocity starts catalysis test through each chamber.Temperature is increased to 230 ℃ and 240 ℃ from 210 ℃, and adjusts synthesis gas flow velocitys at 230 ℃ and 240 ℃, with the conversion ratio obtaining more than 40% at 230 ℃.Following table has provided gathering of the experimental result that obtains.Given conversion ratios in these tables, for CH
4selective and for C
5+optionally value obtain by being averaged experiment value with predetermined distance.By under identical condition, calculate conversion ratio stability divided by initial conversion ratio with final conversion ratio.
Embodiment 1a
Conversion ratio stability=0.84
Embodiment 1b
Conversion ratio stability=0.99
Comparative example A
Conversion ratio stability=0
Comparative example B
Conversion ratio stability=0.68
The main discovery of these experiments gathers as follows:
Compared with comparative example B, Mg is joined to the activity that has reduced catalyst in Co-Ru catalyst, particularly all the more so at 210 ℃.The addition of Mg is higher, and catalyst and comparative example A's activity is lower, and 4.12% Mg is invalid at 210 ℃.But, in embodiment 1a and 1b, add Mg that catalyst stability is increased.Get back to primary condition (210 ℃ and charging in 30ml/ minute) and shown that the catalyst of the Mg that is mixed with 0.5% has lost approximately 3% initial activity, and the catalyst that is mixed with 3% Mg only loses 0.2% initial activity.Although unmodified catalyst has more activity than the catalyst that is mixed with Mg, but after the test condition having experienced 230 ℃ and 240 ℃, it has lost 7% initial activity, and has 0.68 conversion ratio stability, by contrast, the value of embodiment 1a and 1b is respectively 0.84 and 0.99.
B) fixing GHSV.In microreactor, use 0.1g catalyst, but at 16800l/kg
catalystthe fixing GHSV of h gets off to carry out other test.Embodiment 1b and another comparative catalyst are tested.As comparative example B, the Co that comparative example C has comprised the nominal 20% in transition alumina and 0.1% Ru, and prepare by flooding equally.But, be ruthenium acetate for the preparation of the ruthenium compound of this catalyst, and commercially available transition alumina used is HP14/150.The reduction of two kinds of catalyst is all used pure hydrogen to carry out 7h at 380 ℃.At H
2/ CO is than being 2:1, and pressure 20 bar and GHSV are 16800l kg
catalyst -1h
-1test.Result provides in following table, and is presented in Fig. 1,2 and 3.
Fig. 1 has shown the comparative catalyst C performance with respect to the time.This result shows that comparative catalyst C only provides more than 40% conversion ratio, now its rapid deactivation at 250 ℃.Inactivation also can be seen at 240 ℃ and 230 ℃ in Fig. 1.Initial CH
4level is along with temperature has increased by 10, and this shows selective decline, and is maintained at about 15% in the time that initial operating condition (210 ℃) re-establishes.In addition, operating in after 250 ℃, CO conversion ratio is reduced to approximately 4% from initial approximately 9%, and conversion ratio stability is approximately 0.44 in this case.
Fig. 2 and 3 has shown the embodiment 1b performance with respect to the time.In Fig. 2, embodiment 1b has confirmed that at 240 ℃ of conversion ratios be more than 40%, and is stable at the CO conversion ratio of 230 ℃ and 240 ℃.Fig. 2 has also shown that methane level remains on below 10% in whole test process.This test stopped at 100 hours.Carry out retest, and be presented in Fig. 3.In this case, before 210 ℃ of reconstruction operation, the method is directly heated to 240 ℃ from 210 ℃, then to 250 ℃.The conversion ratio of again observing CO in the time of 240 ℃ is approximately 50%, and has produced the CO conversion ratio of 65-70% 250 ℃ of operations.By rebuilding initial operation condition, CO conversion ratio is maintained at about 9%, and methane selectively is not increased to more than 10%.Therefore this test has shown that the catalyst of magnesium doping has kept its initial performance.
Claims (24)
1. the method for the preparation of the synthetic catalyst precarsor of the Fischer-Tropsch that is applicable to hydrocarbon, the cobalt oxide crystallite that this catalyst precarsor comprises 10-40wt% and the noble metal promoted agent of 0.05-0.5wt%, it is dispersed on the surface of porous transition alumina, wherein modification is carried out by the magnesium of including 0.25-3.5wt% in the surface of this transition alumina, and the method comprising the steps of:
(a) form through the catalyst carrier of modification as got off: flood transition alumina with magnesium compound, in the first calcining the temperature of≤600 ℃ dry and calcining through the aluminium oxide of dipping, so that magnesium compound is changed into oxidised form, and
(b) form catalyst precarsor as got off: use cobalt compound and the noble metal promoted immunomodulator compounds dipping catalyst carrier through modification, the dry and catalyst carrier of calcining through flooding in the second calcining, to change into cobalt oxide by cobalt compound.
2. method according to claim 1, wherein this transition alumina comprises gamma-alumina and/or δ aluminium oxide.
3. method according to claim 1 and 2, wherein this transition alumina is pellet or the extrudate of powder or shaping.
4. according to the method described in claim 1-3 any one, wherein this magnesium compound is magnesium nitrate.
5. according to the method described in claim 1-4 any one, wherein this cobalt compound is cobalt nitrate, cobalt acetate or their mixture.
6. according to the method described in claim 1-5 any one, wherein this noble metal promoted immunomodulator compounds is selected from the compound of Pt, Pd, Re, Ru, Ir or Au, preferably the compound of Ru.
7. according to the method described in claim 1-6 any one, wherein this precious metal chemical complex is noble metal acetate or nitrate, comprises nitrosyl radical nitrate.
8. according to the method described in claim 1-7 any one, wherein this cobalt compound and precious metal chemical complex flood simultaneously.
9. according to the method described in claim 1-7 any one, wherein this cobalt compound and precious metal chemical complex flood in succession.
10. according to the method described in claim 1-9 any one, wherein the first calcining is carried out the temperature of≤550 ℃.
11. according to the method described in claim 1-10 any one, and wherein the first calcining is carried out the temperature of >=250 ℃, preferably >=350 ℃, most preferably >=450 ℃.
12. 1 kinds of catalyst precarsors, it can be by obtaining according to the method described in claim 1-11 any one.
The method of 13. 1 kinds of Kaolinite Preparation of Catalysts, it comprises that reduction is according to the step of the prepared catalyst precarsor of claim 1-11 any one.
14. methods according to claim 13, wherein reduction step is carried out with the reducing gas mixture of the mixture that comprises hydrogen, synthesis gas or hydrogen and/or carbon monoxide and nitrogen or other inert gases.
15. methods according to claim 14, the hydrogen that wherein this reducing gas mixture comprises >90 volume %.
16. according to the method described in claims 14 or 15, wherein reduces and carries out the temperature of 350-500 ℃.
17. according to the method described in claim 13-16 any one, and it further comprises and will be encapsulated in the step in chloroflo through the catalyst of reduction.
18. 1 kinds of catalyst, it can be by obtaining according to the method described in claim 13-17 any one.
19. 1 kinds for the synthetic method of the Fischer-Tropsch of hydrocarbon, and it comprises step: by the syngas mixture that comprises hydrogen and carbon monoxide with contact in Fischer-Tropsch reaction device according to the prepared catalyst of the method described in claim 13-17 any one.
20. methods according to claim 19, wherein this Fischer-Tropsch reaction device is fixed bed reactors, slurry phase reactor or micro passage reaction.
21. according to the method described in claim 19 or 20, wherein the hydrogen of this syngas mixture: the ratio of carbon monoxide is 1.6:1-3.0:1, preferably 1.8:1-2.2:1.
22. according to the method described in claim 19-21 any one, and wherein the method is carried out at the pressure of 10-60 bar absolute pressure and the temperature of 210-260 ℃.
23. methods according to claim 22, wherein the method is carried out in the temperature of 230-250 ℃ of scope, and its CO conversion ratio is more than 40%, and C5+ hydrocarbon-selective >=80% and methane selectively≤15%, preferably≤10%.
24. according to the method described in claim 22 or 23, wherein conversion ratio stability >=0.8 of the method, preferably >=0.9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB1117738.3A GB201117738D0 (en) | 2011-10-14 | 2011-10-14 | Cobalt catalyst |
| GB1117738.3 | 2011-10-14 | ||
| PCT/GB2012/052447 WO2013054091A1 (en) | 2011-10-14 | 2012-10-03 | Fischer-tropsch catalyst comprising cobalt, magnesium and precious metal |
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| CN103874539A true CN103874539A (en) | 2014-06-18 |
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| CN201280050291.4A Pending CN103874539A (en) | 2011-10-14 | 2012-10-03 | Fischer-tropsch catalyst comprising cobalt, magnesium and precious metal |
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| Country | Link |
|---|---|
| US (2) | US9346038B2 (en) |
| EP (1) | EP2766114A1 (en) |
| CN (1) | CN103874539A (en) |
| GB (2) | GB201117738D0 (en) |
| WO (1) | WO2013054091A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107999016A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of reactor and its application with three-dimensional channel structure |
| WO2019234554A2 (en) | 2018-06-05 | 2019-12-12 | Sabic Global Technologies B.V. | Iron-magnesium silica supported catalysts, methods of making and uses thereof |
| CN112888500A (en) * | 2018-07-30 | 2021-06-01 | 沙特阿拉伯石油公司 | Catalyst based on mesoporous alumina, containing iron, cobalt and copper on a support, and method for preparing same |
| CN113301991A (en) * | 2019-03-14 | 2021-08-24 | 庄信万丰股份有限公司 | Cobalt catalysts and precursors thereof |
| CN113710361A (en) * | 2019-05-20 | 2021-11-26 | 庄信万丰股份有限公司 | Catalyst preparation method |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102014203877A1 (en) | 2014-03-04 | 2015-09-10 | Wacker Chemie Ag | Catalyst for the Fischer-Tropsch synthesis and process for its preparation |
| WO2017108791A1 (en) * | 2015-12-21 | 2017-06-29 | Shell Internationale Research Maatschappij B.V. | Hydrogenation catalyst and method for preparing the same |
| CA2974159C (en) * | 2016-07-21 | 2019-08-13 | Indian Oil Corporation Limited | A catalyst for co hydrogenation to produce synthesis fuel |
| US11376567B2 (en) * | 2019-12-05 | 2022-07-05 | GM Global Technology Operations LLC | Methods for preparing catalytic systems |
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| US20050234137A1 (en) * | 2002-10-16 | 2005-10-20 | Conocophillips Company | Stabilized boehmite-derived catalyst supports, catalysts, methods of making and using |
| WO2010147513A2 (en) * | 2009-06-16 | 2010-12-23 | Limited Liability Company "Infra Technologies" | Catalyst for synthesis of hydrocarbons from co and h2 and preparation method thereof |
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| EP1569880A4 (en) | 2002-10-16 | 2008-04-09 | Conocophillips Co | Fischer-tropsch processes and catalysts using stabilized supports |
| US7163963B2 (en) | 2003-09-08 | 2007-01-16 | Conocophillips Company | Chemically and thermally stabilized alumina for Fischer-Tropsch catalysts |
| GB2410449B (en) | 2004-01-28 | 2008-05-21 | Statoil Asa | Fischer-Tropsch catalysts |
| GB2473071B (en) | 2009-09-01 | 2013-09-11 | Gtl F1 Ag | Fischer-tropsch catalysts |
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2011
- 2011-10-14 GB GBGB1117738.3A patent/GB201117738D0/en not_active Ceased
-
2012
- 2012-10-03 US US14/347,383 patent/US9346038B2/en not_active Expired - Fee Related
- 2012-10-03 WO PCT/GB2012/052447 patent/WO2013054091A1/en active Application Filing
- 2012-10-03 GB GB1403527.3A patent/GB2509258A/en not_active Withdrawn
- 2012-10-03 EP EP12778776.0A patent/EP2766114A1/en not_active Withdrawn
- 2012-10-03 CN CN201280050291.4A patent/CN103874539A/en active Pending
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2016
- 2016-04-11 US US15/095,277 patent/US20160222301A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050234137A1 (en) * | 2002-10-16 | 2005-10-20 | Conocophillips Company | Stabilized boehmite-derived catalyst supports, catalysts, methods of making and using |
| WO2010147513A2 (en) * | 2009-06-16 | 2010-12-23 | Limited Liability Company "Infra Technologies" | Catalyst for synthesis of hydrocarbons from co and h2 and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107999016A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of reactor and its application with three-dimensional channel structure |
| WO2019234554A2 (en) | 2018-06-05 | 2019-12-12 | Sabic Global Technologies B.V. | Iron-magnesium silica supported catalysts, methods of making and uses thereof |
| CN112888500A (en) * | 2018-07-30 | 2021-06-01 | 沙特阿拉伯石油公司 | Catalyst based on mesoporous alumina, containing iron, cobalt and copper on a support, and method for preparing same |
| CN113301991A (en) * | 2019-03-14 | 2021-08-24 | 庄信万丰股份有限公司 | Cobalt catalysts and precursors thereof |
| CN113301991B (en) * | 2019-03-14 | 2023-10-03 | 庄信万丰股份有限公司 | Cobalt catalyst and precursor thereof |
| CN113710361A (en) * | 2019-05-20 | 2021-11-26 | 庄信万丰股份有限公司 | Catalyst preparation method |
| CN113710361B (en) * | 2019-05-20 | 2023-09-26 | 庄信万丰股份有限公司 | Catalyst preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| GB201403527D0 (en) | 2014-04-16 |
| EP2766114A1 (en) | 2014-08-20 |
| US20140243436A1 (en) | 2014-08-28 |
| GB201117738D0 (en) | 2011-11-23 |
| US9346038B2 (en) | 2016-05-24 |
| US20160222301A1 (en) | 2016-08-04 |
| WO2013054091A1 (en) | 2013-04-18 |
| GB2509258A (en) | 2014-06-25 |
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